WO2005068164A2 - Procede de moulage - Google Patents

Procede de moulage

Info

Publication number
WO2005068164A2
WO2005068164A2 PCT/GB2005/000107 GB2005000107W WO2005068164A2 WO 2005068164 A2 WO2005068164 A2 WO 2005068164A2 GB 2005000107 W GB2005000107 W GB 2005000107W WO 2005068164 A2 WO2005068164 A2 WO 2005068164A2
Authority
WO
WIPO (PCT)
Prior art keywords
soft contact
producing
contact lenses
shaped lens
lens blanks
Prior art date
Application number
PCT/GB2005/000107
Other languages
English (en)
Other versions
WO2005068164A3 (fr
Inventor
Richard Stuart Skipper
Original Assignee
Polymer Sciences Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0400666A external-priority patent/GB0400666D0/en
Priority claimed from GB0422966A external-priority patent/GB0422966D0/en
Priority claimed from GB0425105A external-priority patent/GB0425105D0/en
Priority to MXPA06007990A priority Critical patent/MXPA06007990A/es
Priority to BRPI0506855-0A priority patent/BRPI0506855B1/pt
Priority to US10/597,172 priority patent/US8293154B2/en
Priority to DE602005011569T priority patent/DE602005011569D1/de
Priority to KR1020067015620A priority patent/KR101157487B1/ko
Application filed by Polymer Sciences Limited filed Critical Polymer Sciences Limited
Priority to JP2006548396A priority patent/JP4895822B2/ja
Priority to EP05701875A priority patent/EP1706256B1/fr
Priority to AU2005205097A priority patent/AU2005205097B2/en
Priority to CN2005800022616A priority patent/CN1972796B/zh
Priority to CA2553274A priority patent/CA2553274C/fr
Publication of WO2005068164A2 publication Critical patent/WO2005068164A2/fr
Publication of WO2005068164A3 publication Critical patent/WO2005068164A3/fr
Priority to HK07100489.1A priority patent/HK1093468A1/xx

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00259—Plants for the production of contact lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses

Definitions

  • the present invention relates to a method and apparatus for producing a plurality of ophthalmic lenses such as soft contact lenses and ophthalmic lenses thus produced.
  • the conventional method of producing ophthalmic lenses is to form a lens blank by polymerisation of liquid monomers in a mould and to subsequently mechanically lathe the lens blank into a finished lens and to polish the lens to remove imperfections. This method is labour-intensive and expensive.
  • DSCM double-sided cast moulding
  • controllable moulding process in such a DSCM process is the moulding of the single-use moulds rather than that of the lenses themselves.
  • the most common way of producing the single-use moulds is to produce them between two platens with removably mounted, precisely machined inserts mounted on the platens.
  • a change of mould shape (in order to produce a lens with different optical qualities) is achieved through a change of inserts in the moulding platen.
  • the inserts are generally created on a precision lathe and are polished to remove surface imperfections. Some particular lens optical qualities are created by controlling the orientation of the male to the female mould.
  • US 5,508,317 discloses an improvement to standard DSCM in which an aqueous solution of prepolymer is introduced into the mould and curing is effected by photo-crosslinking. It is claimed that this gives the advantage of allowing the washing/extraction step of standard DSCM to be dispensed with.
  • WO 98/42497 discloses the curing of lenses produced using a DSCM process by the use of UV alone.
  • US 4,673,539 and US 4,786,446 disclose a different production process approach involving creating a shaped thermoplastic hydrogel precursor by the thermoforming of a particular form of uncrosslinked polymer (one containing the product of an ethylenically-unsaturated monomer bearing at least one trihaloacetoxy-substitute group), subsequently solvolyzing the precursor in the presence of a diluent in order to form a polymeric shaped article and finally hydrating the shaped article to provide an ophthalmic lens.
  • This process is claimed to produce lenses with high and controllable water sorbency characteristics .
  • DSCM processes suffer from problems with quality variation in production caused both by control of mould quality in the two- step casting procedure and by variability in the curing process.
  • the curing process is always subject to variations in monomer mixtures and variations in monomer mixture components.
  • a practical curing process is also subject to changes in cure rates due to fluctuations in energy of the (normally thermal) curing source.
  • the method of the current invention provides increased consistency and quality of production as well as a reduction in the quantity of process steps required when compared with prior art methods.
  • the present invention overcomes the problems mentioned above through provision of a method of producing a plurality of soft contact lenses in which a solid, substantially dry material is provided, which is water-soluble above a certain temperature. This material is then formed into a plurality of shaped lens blanks through controlled application of physical force to the material and the shaped lens blanks are subsequently hydrated at a temperature below the certain temperature (above which the material is water-soluble) to form a plurality of soft contact lenses.
  • the present invention also provides an apparatus for producing a plurality of soft contact lenses comprising a forming means for applying a controlled physical force to a sheet of material in order to form a plurality of shaped lens blanks and sheet material transport means comprising driven and/or undriven roller means for transporting a sheet of material.
  • the 'certain temperature' above which the material is water-soluble is either approximately 50°C or approximately 65°C.
  • the material may be: - polyvinyl alcohol or - a copolymer of polyvinyl alcohol and polyvinyl acetate or - polyethylene-maleic-anhydride or - polymethyl-hydroxy-propyl-cellulose or - copolymers of methyl acrylate or - ethyl acrylate with ethylene or their hydroxy derivatives or - a copolymer of polyvinyl alcohol and polyvinyl acetate where the degree of hydrolysis, as measured by saponification, is at least 96% mol based on the original polyvinyl alcohol.
  • the material is a substantially uncrosslinked polymer comprising crosslinkable groups .
  • high energy is applied to the shaped lens blanks , crosslinking the polymer to a predetermined, desired crosslink density .
  • the polymer may also contain additives that react to the application of high energy to improve crosslinking efficiency .
  • High energy ' may be in any of the following forms : electron beam irradiation or - gamma irradiation or - microwave irradiation or - ultraviolet irradiation or - infrared irradiation or thermal irradiation or - ultrasound irradiation.
  • the material is provided in as a sheet of material and the shaped lens blanks remain at least partially attached to this sheet of material after the physical forming step B.
  • a further desirable implementation for such a method is to remove the shaped lens blanks from the sheet, at the appropriate point in the process using a laser cutting device.
  • the physical forming step B may be carried out using a number of different processes such as: thermoforming or - vacuum forming or - pressing or hot moulding or - cold moulding or - compression moulding or injection moulding.
  • thermoforming embodiment of the method of the invention the material is heated to a temperature that is near to the softening temperature of the material, so that thermoforming of the material is possible, but is below the melting point of the material, so that the physical integrity of the material is maintained.
  • Thermoforming of the shaped lens blanks is then carried out through application of physical force to the heated material.
  • the physical force might be applied by compressing the material between two forms or platens.
  • the physical forming step B uses moulds. The material is placed between the moulds and these are pressed together to form said plurality of shaped lens blanks.
  • the shaped lens blanks are transferred to a plurality of final packs.
  • These final packs may be pre-sterilised. They may also contain the aseptic or sterile solution, which acts to hydrate the lenses in step C. In some such embodiments the material of the shaped lens blanks may undergo a chemical reaction, such as hydrolysis, in the final pack.
  • step B all process steps after step B are carried out without further human contact or handling.
  • the method may thus be automated or semi-automated to run in a continuous or semi-continuous manner.
  • quality control inspections are carried out on the shaped lens blanks only. These inspections may be either visual or may use an optical system.
  • the invention also provides a method of producing a plurality of ophthalmic lenses, which comprises (a) providing a substantially uncrosslinked polymer, comprising crosslinkable groups; (b) physically forming this polymer into a plurality of ophthalmic lenses; and (c) applying high energy to the plurality of ophthalmic lenses thus crosslinking the polymer to a predetermined, desired crosslink density.
  • the forming means comprises a plurality of forms or platens arranged so that they press together to form the sheet of material into a plurality of shaped lens blanks.
  • This plurality of forms or platens may be provided with heating means to heat the sheet of material to make the forming process easier.
  • the plurality of platens are removably connectable with a plurality of male and female inserts.
  • These male and female inserts are formed to appropriate shapes to form the shaped lens blanks to desired optical specifications.
  • the inserts may be arranged such that pressure (either positive or negative) may be applied through them.
  • the apparatus further comprises packaging means for transferring said shaped lens blanks into final packs.
  • This packaging means may be arranged to carry out packaging in a substantially sterile environment.
  • the apparatus of the invention also comprises a removing means for removing the shaped lens blanks from the sheet of material and for forming the circumferential edges of the shaped lens blanks.
  • This removing means may be a laser cutting means such as a C02 laser.
  • Some preferred embodiments of the apparatus provided by the invention also comprise high energy application means for applying high energy to the shaped lens blanks and/or to soft contact lenses formed from the shaped lens blanks. This high energy application means could be an electron beam irradiation means .
  • lenses produced using the current invention have an improved accuracy of lens power, improved surface quality and improved power consistency vis-a-vis those produced using prior art methods.
  • Some particular embodiments of the current invention provide improved sterilisation, packaging and in-line inspection steps over prior art methods of production. These improvements can also lead to a reduced manufacturing area requirement.
  • the current invention has the advantage that mould washing and inspections for mould cleanliness is not required as frequently .
  • UV- absorbing agents cannot be incorporated into lenses , since these then inhibit the polymerisation process .
  • non-UV forms of irradiation may be employed when it is desired to create lenses containing such UV-absorbing agents .
  • Figure 1 A schematic diagram of a contact lens manufacturing apparatus according to an embodiment of the invention
  • Figure 1 shows a schematic representation of an embodiment of the invention.
  • a roll of polymer in the form of sheet, 1 is provided and is transported to a thermoforming area, 14.
  • the polymer sheet Prior to entering the thermoforming area the polymer sheet is inspected by means of an automatic vision system, 2 , for significant defects , such as tears , that would result in an unsatisfactory final product.
  • the polymer may be Mowiol® (a material made by Clariant GmbH) - a copolymer of polyvinyl alcohol and polyvinyl acetate where the degree of hydrolysis, as measured by saponification, is at least 96% mol based on the original polyvinyl alcohol.
  • the polymer sheet is heated to a temperature where it is easy to shape the polymer into the desired shape as defined by inserts on the moulding platens, 3 and 9, in the thermoforming process and yet the polymer sheet still retains sufficient strength for it to be manipulated through the process.
  • the polymer sheet is then passed through the thermoforming area where platens, 3 and 9, containing optical quality inserts (not shown), shape the polymer sheet into the desired form.
  • the inserts and the platens may be cooled or heated as required to obtain the required flow and optical clarity in the shaped part.
  • the use of pressure or vacuum through the platens or inserts may also be used to achieve the desired shape.
  • the optical inserts and their bodies, which fit into the platen, are so designed that the formed parts are not fully detached from the original polymer sheet and so that after the forming process has been completed the formed parts are moved forward with the polymer sheet, 12.
  • the formed parts are then inspected by means of an automated vision system, 4, for defects.
  • the polymer sheet with formed parts may then be stored for use in the future or processed immediately as a continuous or semi-continuous process by passing it through a sterilising electron beam at station 5.
  • the exposure of the polymer sheet and the formed parts to an electron beam may be so controlled that the polymer becomes as crosslinked as is required as well as as sterile as is required.
  • the formed parts are separated from the polymer sheet and deposited into final packages within a sterile environment — schematically shown as occurring at station 5 in figure 1, although it is to be noted that packaging may occur at a separate station from electron beam irradiation (not shown) .
  • the final packages are manufactured and/or treated at station 6 so that they are effectively sterile and are maintained within an environment that keeps them, and the formed parts, sterile.
  • the final packages are transported, 13, to a position to allow transfer of the formed parts into the final packages.
  • the final packages holding the formed parts are transported within the sterile environment to a dosing station, 7, where aseptic or sterile packaging/hydration solution is added — controlled to be at a temperature below the temperature at which the polymer becomes water-soluble.
  • the final packages, solution and formed parts are then sealed at station, 8, also within the sterile area, with a sterile foil before leaving the process area for final labelling.
  • Opt lenses refers to any medical or vision correction devices that are used in the ocular environment, including contact lenses, intraocular lenses, corneal onlays and inlays, ocular drug delivery devices, ocular wound healing devices and the like.
  • a crosslinking portion of the lens production process involves the exposure of a dry lens shape made from the polymer to a high energy source.
  • High energy refers to many different forms and includes sources that generate, but is not limited to, thermal, I.R., U.V., microwave, gamma, ultrasonic and electron beam radiation.
  • Crosslinking is used to describe the process in which a soluble polymer is converted into an insoluble form through the formation of bonds, i.e. crosslinks, between the polymer chains. It will be obvious to those skilled in the art that the insoluble form may, in addition to crosslinked structures, contain structures known as grafted polymers or entangled polymers.
  • One purpose of crosslinking, as used herein, is to permit the crosslinked dry lens to form a stable wet lens, as required by the design, and in doing so provide power correction to a wearer.
  • the crosslinked polymer is known as a hydrogel.
  • Polymer refers to the material from which the initial lens shape is produced and includes copolymers, mixtures of polymers, interpenetrating network systems, polymer systems that are already partially crosslinked, polymer to which additives have been added to assist in the crosslinking reaction, to reduce UV transmission, for therapeutic purposes, to add colour for cosmetic reasons and the like.
  • the energy source and radiation used for any crosslinking may vary, together with time of exposure, depending on the polymer composition and the properties required.
  • the final lens may comprise water content from 20 to 75%, by weight. It can be generally assumed that for a given polymer the crosslink density of the lens will control the water content of the lens, i.e. the greater the crosslink density the lower the water content.
  • any crosslinking process is achieved as quickly as possible, preferably in less than 10 minutes, more preferably in less than 4 minutes, and even more preferably in less than one minute.
  • additives may be incorporated into the polymer at a level of 0.2 to 5% by weight for the purpose of promoting crosslinking.
  • These compounds may be poly-functional vinyl or allyl compounds such as triallyl cyanurate, triallyl isocyanurate or pentaerithritol tetramethacrylate.
  • Radiation dosages will depend on the response of the polymer being irradiated and on the level, if any, of prorad. Typical dosages will be in the range 20 to 800 kGy, preferably 20 to 500 kGy, e.g. 20 to 200 kGy and particularly 40 to 120 kGy.
  • the finished, packaged lens may also be sterilised by any other appropriate means (e.g. ETO, gamma, steam etc.). Although the means of sterilisation will have to be carefully selected so as not to significantly change the properties or performance of the lens or package.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ophthalmology & Optometry (AREA)
  • Mechanical Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Eyeglasses (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Glass Compositions (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Méthode et appareil extrêmement efficaces et économiques de fabrication de lentilles souples de contact par façonnage physique des lentilles dans une feuille de matériau (ou autre matériau solide) par lots ou en continu.
PCT/GB2005/000107 2004-01-13 2005-01-13 Procede de moulage WO2005068164A2 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
AU2005205097A AU2005205097B2 (en) 2004-01-13 2005-01-13 Moulding process
CN2005800022616A CN1972796B (zh) 2004-01-13 2005-01-13 模制方法
CA2553274A CA2553274C (fr) 2004-01-13 2005-01-13 Procede de moulage
EP05701875A EP1706256B1 (fr) 2004-01-13 2005-01-13 Procede de moulage
US10/597,172 US8293154B2 (en) 2004-01-13 2005-01-13 Moulding process
DE602005011569T DE602005011569D1 (de) 2004-01-13 2005-01-13 Formverfahren
KR1020067015620A KR101157487B1 (ko) 2004-01-13 2005-01-13 몰딩 공정
MXPA06007990A MXPA06007990A (es) 2004-01-13 2005-01-13 Proceso de moldeo.
JP2006548396A JP4895822B2 (ja) 2004-01-13 2005-01-13 成形プロセス
BRPI0506855-0A BRPI0506855B1 (pt) 2004-01-13 2005-01-13 Método de produção de uma pluralidade de lentes de contato moles
HK07100489.1A HK1093468A1 (en) 2004-01-13 2007-01-15 Moulding process

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB0400666.4 2004-01-13
GB0400666A GB0400666D0 (en) 2004-01-13 2004-01-13 Moulding process
GB0422966A GB0422966D0 (en) 2004-10-18 2004-10-18 Removal of moulded parts
GB0422966.2 2004-10-18
GB0425105.4 2004-11-15
GB0425105A GB0425105D0 (en) 2004-11-15 2004-11-15 Moulding process

Publications (2)

Publication Number Publication Date
WO2005068164A2 true WO2005068164A2 (fr) 2005-07-28
WO2005068164A3 WO2005068164A3 (fr) 2005-09-15

Family

ID=34799124

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2005/000107 WO2005068164A2 (fr) 2004-01-13 2005-01-13 Procede de moulage

Country Status (12)

Country Link
US (1) US8293154B2 (fr)
EP (1) EP1706256B1 (fr)
JP (1) JP4895822B2 (fr)
KR (1) KR101157487B1 (fr)
AT (1) ATE416907T1 (fr)
AU (1) AU2005205097B2 (fr)
BR (1) BRPI0506855B1 (fr)
CA (1) CA2553274C (fr)
DE (1) DE602005011569D1 (fr)
HK (1) HK1093468A1 (fr)
MX (1) MXPA06007990A (fr)
WO (1) WO2005068164A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0611443D0 (en) * 2006-06-09 2006-07-19 Powderject Res Ltd Improvements in, or relating to, particle cassettes
JP5618053B2 (ja) * 2010-03-24 2014-11-05 株式会社日本コンタクトレンズ コンタクトレンズ、及びその製造方法
US9481124B2 (en) 2013-03-15 2016-11-01 Johnson & Johnson Vision Care, Inc. Method and apparatus for forming thermoformed ophthalmic insert devices
US20210162692A1 (en) * 2019-12-02 2021-06-03 Bausch & Lomb Ireland Limited Direct compression molded ophthalmic devices
WO2021191657A1 (fr) * 2020-03-23 2021-09-30 Gilia Andrei Procédé pour la fabrication de tous types de lentilles de contact rigides perméables aux gaz

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2119957A (en) * 1982-04-29 1983-11-23 Agripat Sa Annealed polyvinyl alcohol contact lens
EP0131227A2 (fr) * 1983-07-12 1985-01-16 Bayer Ag Procédé de fabrication d'articles optiques de contact
US4786446A (en) * 1985-05-17 1988-11-22 Minnesota Mining And Manufacturing Company Process of forming a hydroxy-substitute polymeric shaped article

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GB699014A (en) 1949-03-28 1953-10-28 Mueller Welt G M B H Improved manner of manufacture of contact lenses
GB819474A (en) 1955-05-13 1959-09-02 Frederick Thomas Ridley Contact lenses
US4402579A (en) * 1981-07-29 1983-09-06 Lynell Medical Technology Inc. Contact-lens construction
GB2105866B (en) 1981-07-29 1985-05-09 Lynell Med Tech Inc Intraocular and extraocular lens construction and making by selective erosion
JPS60108408A (ja) 1983-11-16 1985-06-13 Asahi Chem Ind Co Ltd 共役ジエン重合体の製造法
US4652721A (en) 1985-01-03 1987-03-24 Dow Corning Corporation Method and apparatus for edge contouring lenses
JPH02235729A (ja) * 1989-03-10 1990-09-18 Hitachi Ltd プラスチック光学部品の製造方法およびその装置
US5166528A (en) * 1991-10-04 1992-11-24 Le Vay Thurston C Microwave-actuated ultraviolet sterilizer
JPH0767735B2 (ja) * 1992-02-18 1995-07-26 岐阜プラスチック工業株式会社 真空成形品の打抜き方法
US5597519A (en) 1994-06-10 1997-01-28 Johnson & Johnson Vision Products, Inc. Ultraviolet cycling oven for polymerization of contact lenses
JP3623575B2 (ja) * 1995-12-28 2005-02-23 三菱樹脂株式会社 プラスチックシートの熱成形装置及び熱成形方法
US6113817A (en) * 1997-03-25 2000-09-05 Novartis Ag Molding processes
AU731550B2 (en) 1997-03-25 2001-04-05 Novartis Ag Molding processes
US20040112008A1 (en) * 1998-12-21 2004-06-17 Voss Leslie A. Heat seal apparatus for lens packages
WO2001015497A1 (fr) 1999-08-23 2001-03-01 Bausch & Lomb Incorporated Procede et systeme de polymerisation regulee utilises dans la production de lentilles de contact
US6474465B1 (en) * 1999-11-19 2002-11-05 Novartis Ag Blister package
US6765661B2 (en) * 2001-03-09 2004-07-20 Novartis Ag Lens inspection

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2119957A (en) * 1982-04-29 1983-11-23 Agripat Sa Annealed polyvinyl alcohol contact lens
EP0131227A2 (fr) * 1983-07-12 1985-01-16 Bayer Ag Procédé de fabrication d'articles optiques de contact
US4786446A (en) * 1985-05-17 1988-11-22 Minnesota Mining And Manufacturing Company Process of forming a hydroxy-substitute polymeric shaped article

Also Published As

Publication number Publication date
JP2007520373A (ja) 2007-07-26
US8293154B2 (en) 2012-10-23
BRPI0506855B1 (pt) 2015-08-11
US20080315444A1 (en) 2008-12-25
EP1706256B1 (fr) 2008-12-10
CA2553274C (fr) 2013-03-12
EP1706256A2 (fr) 2006-10-04
BRPI0506855A (pt) 2007-05-29
AU2005205097B2 (en) 2010-08-05
AU2005205097A1 (en) 2005-07-28
WO2005068164A3 (fr) 2005-09-15
KR20060126756A (ko) 2006-12-08
KR101157487B1 (ko) 2012-07-06
ATE416907T1 (de) 2008-12-15
HK1093468A1 (en) 2007-03-02
DE602005011569D1 (de) 2009-01-22
CA2553274A1 (fr) 2005-07-28
MXPA06007990A (es) 2007-01-26
JP4895822B2 (ja) 2012-03-14

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